Metal ion control agents based on dicyclopentadiene derivatives

ABSTRACT

New compounds have been prepared from dicyclopentadiene bis(methylamine) which have the following formula ##STR1## wherein substituents A, B, X and Y each are independently selected from radicals including hydrogen, hydroxyalkyl (wherein the alkyl group contains 2-6 carbon atoms) phosphonic, sulfonic, hydroxyethyl- and hydroxypropylsulfonic, methylenephosphonic methylene-, ethylene- and propylenesulfonic, alkylcarboxylic acid radicals (having 2-4 carbon atoms) and the alkali or alkaline earth metal, ammonia and amine salts of any of the phosphonic, sulfonic or carboxylic acid derivatives. At least one of the substituents must be other than a hydrogen. These compounds are useful chelating agents and those containing the methylenephosphonic substituents are good threshold agents.

This is a divisional of application Ser. No. 486,122, filed Apr. 18,1983, now U.S. Pat. No. 4,500,470.

BACKGROUND OF THE INVENTION

Dicyclopentadiene (DCPD) is a relatively plentiful diunsaturated monomerwith a variety of potential uses due to the ease of making derivativesby reaction with the double bonds. Its source is the bottoms of lighthydrocarbon distillation columns wherein it is formed by prolongedheating of the C₅ fraction. It has the following structure ##STR2##

Reactions are known to form the nitrile or dinitrile by reacting thedouble bonds of DCPD with HCH; the nitrile can then be hydrolyzed toform the carboxylic acid derivative. The DCPD can also be catalyticallyreacted with HCN, followed by reduction to obtain the bis methylaminederivative; this product in turn can be reacted with glycolonitrile inthe presence of caustic to give the sodium salt of tetraacetic acid ofthe bis amine, a likely chelating agent since it resembles EDTA.

It is well known that amines such as ethylenediamine anddiethylenetriamine can be reacted with formaldehyde and phosphorus acidto obtain methylene phosphonate derivatives of the amine in which themethylene phosphonate group ##STR3## substitutes for the amine hydrogens(U.S. Pat. No. 3,288,846).

The use of methylenephosphonic acid substituted alkylene polyamines formetal ion control at less than stoichiometric amounts was suggested in apatent (U.S. Pat. No. 2,609,390) issued in 1952. Later a waterdispersible polymeric amine chelating agent which included alkylenephosphonate derivatives was indicated as having "threshold" effects inscale inhibition applications (see U.S. Pat. No. 3,331,773), this termbeing used to describe the use of the agent in less than stoichiometricamounts. The diamine and polyamine methylenephosphonate derivatives aretaught and claimed in U.S. Pat. Nos. 3,336,221 and 3,434,969,respectively. Some of the products disclosed in these two patents areavailable commercially and are recommended as scale inhibitors whenapplied in threshold amounts.

Other patents which disclose heterocyclic nitrogen containing compoundswhich are useful as chelating agents and may be employed in thresholdamounts are U.S. Pat. Nos. 3,674,804; 3,720,498; 3,743,603; 3,859,211;and 3,954,761. Some of the compounds included therein are heterocycliccompounds having the formulas: ##STR4## wherein R is hydrogen or alkyland M is hydrogen, alkali metal, ammonium or a di- or triethanolamineradical;

Methylenephosphonates of polyalkylene polyamines, disclosed in U.S. Pat.No. 4,051,110, are made by reacting di- or polyamines with a chainextending agent such as a dihalide or an epoxyhalide, e.g. ethylenedichloride or epichlorohydrin and thereafter, with phosphorus acid andformaldehyde. Thus, for example, triethylenetetramine is reacted withepichlorohydrin in an approximately one to one mole ratio; thereafterthe product is reacted with phosphorus acid, and formaldehyde in thepresence of hydrochloric acid. The resulting methylenephosphonatedpolyamine is useful in small amounts as a scale inhibitor, beingemployed at concentrations of 20-50 ppm.

Certain phosphonic acid derivatives of the aliphatic acids can beprepared by reacting phosphorus acid with acid anhydrides or acidchlorides, e.g. the anhydrides or chlorides of acetic, propionic andvaleric acids. The compounds prepared have the formula ##STR5## whereinR is a lower alkyl radical having 1 to 5 carbon atoms. The method ofmaking and use of these products is described in U.S. Pat. No.3,214,454. The use of threshold amounts to prevent calcium precipitationis disclosed and claimed therein.

It has now been discovered that new chelating and threshold agents forinhibiting precipitation of metal ions can be made from thebis(methylamine) derivatives of dicyclopentadiene. They can also beconsidered as tricyclodecane derivatives. Thus, dicyclopentadienebis(methylamine) can be named 3(4),8(9)-bis(aminomethyl)-tricyclo[5.2.1.0²,6 ]decane.

SUMMARY OF THE INVENTION

A new class of compounds is formed when dicyclopentadienebis(methylamine) is reacted with certain compounds, e.g. formaldehydeand phosphorous acid will form methylenephosphonic acid derivatives.These new compounds have the structure ##STR6## wherein substituents A,B, X and Y each are independently selected from radicals includinghydrogen, hydroxyalkyl (wherein the alkyl group contains 2-6 carbonatoms) phosphonic, sulfonic, methylenephosphonic, methylene-, ethylene-and propylene-sulfonic, carboxylic acid radicals (having 2-4 carbonatoms) and the alkali or alkaline earth metal, ammonia and amine saltsof any of the phosphonic, sulfonic or carboxylic acid derivatives. Atleast one of the substituents must be other than a hydrogen.

DETAILED DESCRIPTION OF THE INVENTION

When formaldehyde and phosphorus acid are reacted with DCPDbis(methylamine), hereinafter DCPD-BMA, the result in a new compoundhaving the following structure: ##STR7##

The above compound has been found to have excellent thresholdproperties.

Other substituents for the hydrogens of the amine groups of the aboveDCPD derivatives form useful chelating agents, but only themethylenephosphonic acid substituted compounds and their alkali,alkaline earth metal, ammonia or amine salt derivatives are effective asthreshold agents.

Substituents other than methylenephosphonates give compounds having thefollowing structure: ##STR8## wherein A, B, X, Y can be hydrogen,hydroxyalkyl, wherein the alkyl group contains 2 to 6 carbon atoms,hydroxyethyl- and hydroxypropylsulfonic, phosphonic, sulfonic,methylene-, ethylene- and propylenesulfonic, alkylcarboxylic acidradicals, and their alkali or alkaline earth metal, ammonia or aminesalts, with the proviso that at least one of the groups must be otherthan hydrogen.

The following examples illustrate the preparation of the new compounds.

EXAMPLE 1

Deionized water (100 g) and 49.0 g (0.25 mole) of DCPD-BMA weighed intoa 500 ml round-bottom reaction flask equipped with a water-cooled refluxcondenser, mechanical stirrer, thermometer with a temperaturecontroller, and an addition funnel. Approximately 120 g of concentratedHC1 solution and 98.7 g (1.20 mole) of phosphorous acid were added tothe aqueous amine solution and the reaction mixture heated to reflux andmaintained for one hour. Aqueous 37% formaldehyde solution (85.1 g, 1.05mole) was added to the addition funnel and added over a two hour period.The reaction mixture was heated at reflux for an additional two hoursand then cooled. The product obtained was the DCPD-BMA derivative inwhich each amine hydrogen is replaced by a methylenephosphonic acidgroup ##STR9##

EXAMPLE 2

The procedure of Example 1 was followed except 0.60 mole of phosphorousacid and 0.53 mole of aqueous formaldehyde solution were used. Theproduct obtained was the DCPD-BMA derivative in which there are twomethylenephosphonic acid group substituents with two hydrogens remainingunsubstituted.

EXAMPLE 3

The procedure of Example 2 was repeated and the reaction productcarboxymethylated using 0.55 mole of aqueous glycolonitrile (HOCH₂C.tbd.N) in the presence of excess caustic to produce the sodium salt ofthe aminocarboxylic acid. The product obtained was the DCPD-BMAderivative containing two methylene sodium phosphonate and two sodiumacetate groups.

EXAMPLE 4

Deionized water (40 g) and 24.5 g (0.125 mole) of DCPD-BMA were weighedinto a 500 ml round-bottom flask equipped with a water-cooled refluxcondenser, mechanical stirrer, thermometer with a temperaturecontroller, and an addition funnel. Caustic solution (10.1 g of 50%) and25.0 g (0.127 mole) the sodium salt of3-chloro-2-hydroxy-1-propanesulfonic acid, were added with stirring andthe reaction mixture heated at 85° C. for one hour. Additional causticsolution (12.0 g of 50%) and 25.0 g of the sodium salt of3-chloro-2-hydroxy-1-propanesulfonic acid, were then added and thesolution heated at 85° C. for 11/2 hours. Approximately 60 g ofconcentrated HCl solution and 24.7 g (0.300 mole) of phosphorous acidwere added and the reaction mixture heated to reflux and maintained forone hour. Aqueous 37% formaldehyde solution (21.3 g, 0.263 mole) wasadded to the addition funnel and added over about a one-hour period. Thereaction mixture was heated at reflux for an additional three hours andthen cooled. The product obtained was the DCPD-BMA derivative containingtwo methylenephosphonic acid and two 2-hydroxypropylsulfonic acid andtwo 2-hydroxypropylsulfonic acid groups --H₂ C-CHOH-CH₂ -SO₃ H.

EXAMPLE 5

The procedure of Example 4 was followed except 0.127 mole of the sodiumsalt of 3-chloro-2-hydroxy-1-propanesulfonic acid, 37.0 g (0.350 mole)of phosphorus acid, and 32.0 g (0.3944 mole) of 37% formaldehydesolution were used. The product obtained was the DCPD-BMA derivativecontaining three methylenephosphonic acid groups and one2-hydroxypropylsulfonic acid group.

EXAMPLE 6

Deionized water (40 g) and 24.5 g (0.125 mole) of DCPD-BMA were weighedinto a 500 ml round-bottom reaction flask equipped with a water-cooledreflux condenser, mechanical stirrer, thermometer with a temperaturecontroller, and an addition funnel. Caustic solution (10.1 g of 50%) and25.0 g (0.127 mole) of the sodium salt of3-chloro-2-hydroxyl-1-propanesulfonic acid, were then added and heatingcontinued for one hour at 85° C. The addition of caustic solution and ofthe sodium salt 3-chloro-2-hydroxy-1-propanesulfonic acid, was repeatedthree more times as outlined above except that the reaction solution wasmaintained at 85° C. for two hours after each addition. The productobtained was the DCPD-BMA derivative containing four 2-hydroxypropylsodium sulfonate groups, i.e. all amine hydrogens were substituted withthat same group.

EXAMPLE 7

Ethylene oxide (11.6 g, 0.263 mole) was reacted with 24.5 g (0.125 mole)of DCPD-BMA and the reaction product then phosphonomethylated accordingto the procedure of Example 1 using 0.300 mole of phosphorous acid and0.263 mole of formaldehyde solution. The product obtained was theDCPD-BMA derivative containing two hydroxyethyl and twomethylenephosphonic acid groups.

EXAMPLE 8

The procedure of Example 7 was followed except that amine was reactedwith 0.132 mole of ethylene oxide and the reaction productphosphonomethylated using 0.450 mole of phosphorous acid and 0.394 moleof formaldehyde solution. The product obtained was the DCPD-BMAderivative containing one hydroxyethyl group and threemethylenephosphonic acid groups.

EXAMPLE 9

Propylene oxide (7.6 g, 0.130 mole) was reacted with 24.5 g (0.125 mole)of DCPD-BMA and the reaction product then phosphonomethylated accordingto the procedure of Example 1 using 0.450 mole of phosphorous acid and0.394 mole of formaldehyde solution. The product obtained was the sameas that of Example 8 except for a hydroxypropyl group in place of thehydroxyethyl group.

EXAMPLE 10

Sodium bisulfite (13.7 g, 0.131 mole) and 15 g of distilled water wereadded to a round-bottom reaction flask equipped with a water-cooledreflux condenser, mechanical stirrer, thermometer with a temperaturecontroller, and an addition funnel. Formaldehyde solution (10.7 g of 37%0.131 mole) was added to the addition funnel and added with stirring tothe sodium bisulfite-water mix over a 5-minute period. The reactionproduct was then heated to 75° C. for one-half hour and then cooled. Thesodium bisulfite-formaldehyde reaction solution was transferred to theaddition funnel and 24.5 g (0.125 mole) of DCPD-BMA and 20 g ofdistilled water added to the reaction flask. The amine solution washeated to 75° C. and the sodium bisulfite-formaldehyde solution addedover a one-hour period and then heated at 75° C. for three hours.Concentrated HCl (75 g) and 37 g (0.450 mole) of phosphorous acid wereadded to the flask and the mixture heated to 100° C. Formaldehydesolution (32.0 g, 0.394 mole) was added to the addition funnel and addedover a 20-minute period. The reaction mixture was heated at 100° C. for40 minutes and then at reflux for an additional three hours beforecooling. The product obtained was the DCPD-BMA derivative containing onemethylenesulfonic acid group and three methylenephosphonic acid groups.

It should be recognized that when mixed derivatives are obtained, it isnot usually possible to direct or predict which amine hydrogens aresubstituted. The product, in all probability, contains a mixture ofisomeric compounds.

To show the usefulness of the compounds of the present invention, thefollowing test was run to determine calcium scale inhibition:

Several 50 ml samples of a 0.02M CaCl₂ solution were placed in 4-oz.bottles. To these solutions was added the candidate inhibitor in variousconcentrations. Fifty-ml samples of a 0.04M sodium bicarbonate/0.96Msodium chloride solution were then added with stirring. A total hardnessdetermination was made on the mixture by adding excess standard EDTA andback titrating with standard Mg⁺⁺ solution in the presence of EriochromeBlack T indicator. The samples were placed in an 80° C. oven and 10-mlsamples taken periodically from each bottle, filtered through amillipore filter, and the total hardness of the filtrates determined bytitration. A blank with no inhibitor was run in an identical manner. Thepercent inhibition was calculated from the total hardness before heatingand the total hardness found after heating at 80° C. for 24 hours.

Table I shows results obtained with the compounds of the presentinvention compared to two of the more widely used commercially availableorganophosphonate scale inhibitors.

                  TABLE I                                                         ______________________________________                                        Scale Inhibition Data                                                                             Concen-  % Inhibi-                                        Compound Used       tration* tion                                             ______________________________________                                        None                --        7.2                                             Example 1           10 ppm   43.4                                             Example 2           10 ppm   29.0                                             Example 3           10 ppm   35.5                                             Example 4           10 ppm   40.2                                             Example 5           10 ppm   39.0                                             Example 6           10 ppm   24.2                                             Example 7           10 ppm   27.7                                             Example 8           10 ppm   42.8                                             Example 9           10 ppm   43.8                                             Example 10          10 ppm   42.2                                             Aminotri(methylenephosphonic                                                                      10 ppm   39.3                                             acid) pentasodium salt                                                        1-hydroxyethylidene-1,1-                                                                          10 ppm   40.3                                             diphosphonic acid                                                             ______________________________________                                         *ppm based on active acid                                                

The usefulness of the compounds of the present invention to act aschelating agents was demonstrated by preparing iron chelate solutionsthat were 0.01M in ferric iron. Fifty ml aliquots were taken and the pHadjusted with aqueous ammonia to approximately 7.5, 8.3, 9.0, and 10.0.The samples were allowed to stand for about two weeks and then solubleiron determined by analyzing the clear overhead. The data obtained forthree of the compounds of the present invention is summarized in TableII and compared with two commercially available chelating agents.

                  TABLE II                                                        ______________________________________                                                     Percent of Total Iron                                                   Molar Remaining in Solution at pH                                      Chelant Used                                                                           Concn.  7.5     8.3     9.0   10.0                                   ______________________________________                                        None     --      <1.0    <1.0    <0.5  <0.2                                   Example 1                                                                              0.01    100     91.1    100   100                                    Example 5                                                                              0.01    71.0    91.0    100   14.4                                   Example 8                                                                              0.01    78.6    87.5    87.5  92.9                                   Glycolic acid                                                                          0.04    96.2    <0.2    <0.2  <0.2                                   Glycolic acid                                                                          0.10    96.2    96.2    <0.5  <0.2                                   Glycolic acid                                                                          0.20    94.3    96.2    24.5  <0.5                                   HEIDA*   0.01    100     100     100   28.3                                   ______________________________________                                         *HEIDA = N--hydroxyethyliminodiacetic acid                               

I claim:
 1. A process for inhibiting the precipitation of alkaline earthmetal ions from their aqueous solutions which comprises adding to saidsolutions in less than stoichiometric amounts, based on the metal ionspresent, a compound of the formula ##STR10## wherein substituents A, B,X and Y are each independently selected from radicals includinghydrogen, hydroxyalkyl (wherein the alkyl group contains 2-6 carbonatoms) phosphonic, sulfonic, hydroxyethyl- and hydroxypropylsulfonicmethylenephosphonic, methylene-, ethylene- and propylenesulfonic,alkylcarboxylic acid radicals (having 2-4 carbon atoms) and the alkalior alkaline earth metal, ammonia and amine salts thereof and wherein atleast one of said substituents is a methylenephosphonic acid radical ora salt thereof.
 2. The process of claim 1 wherein the substituent saltof the methylenephosphonic acid radical is an alkali metal salt.
 3. Theprocess of claim 1 wherein the substituent salt of themethylenephosphonic acid is an amine salt.
 4. The process of claim 1wherein the substituent salt of the methylenephosphonic acid is analkaline earth metal salt.
 5. The process of claim 4 wherein thealkaline earth metal is magnesium, calcium or barium.
 6. The process ofclaim 1 wherein the substituent salt of the methylenephosphonic acid isan ammonium salt.
 7. A process for chelating metal ions in an aqueoussolution thereof which comprises adding thereto at least astoichiometric amount based on the metal ions present, of a compound,having the following formula ##STR11## wherein substituents A, B, X andY each are independently selected from radicals including hydrogen,hydroxyalkyl (wherein the alkyl group contains 2-6 carbon atoms)phosphonic, sulfonic, hydroxyethyl- and hydroxypropylsulfonic,methylenephosphonic, methylene-, ethylene- and propylenesulfonic,alkylcarboxylic acid radicals (having 2-4 carbon atoms) and the alkalior alkaline earth metal, ammonia and amine salts thereof and wherein atleast one A, B, X and Y is other than hydrogen.
 8. The process of claim7 wherein A, B, X and Y are each methylenephosphonic acid radicals. 9.The process of claim 8 wherein the acid radicals are in a salt form.